Thiocyano aliphatic acid esters of endoethylene-hydroxycyclopentanoindane



Patented Feb. 12, 1946 THIOCYANO ALIPHATIC ACID ESTERS OF ENDOETHYLENE HYPROXYCYCLQPEN TANOINDANE Herman A. Bruson, Philadelphia, Pa., assignor to The Resinous Products & Chemical Company, Philadelphia, Pa., a corporation of Delaware No Drawing. Application September 12, 1944,

Serial No. 553,799

5 Claims.

This invention relates to esters of thiocyano aliphatic carboxylic acids and 3,5-endoethylene hydroxycyclopentanoindane. These esters are new compounds having the formula new thiocyano esters which are specifically claimed in the present specification.

The new compounds are advantageously prepared by reacting a halogenated aliphatic carbozrylic acid preferably in the presence of an acidic condensing agent, with 1,4-endomethylene tetrahydro-A -fiuorene to form an ester of endoethylene hydroxycyclopentanoindane by an addihon-rearrangement reaction and replacing the halogen atom with a thiocyano radical. Alternatively, the new compounds of this invention are prepared by esterifying the new compound, 3,5 endoethylene hydroxycyclopentano -4,5- indane, with a halo aliphatic carboxylic acid and replacing the halogen with a thiocyano radical.

Thus, in accordance with the first method mentioned above, 1,4-endomethylene tetrahydro-zl fiuorene reacts with a halo aliphatic carboxylic acid, XACOOH, where X represents bromine or chlorine, as follows:

ln CH XACOOH j: a Ag iii The halogen atom may now be ethyl alcohol, propyl or isopropyl alcohol, acetone, -or similar volatile organic. solvents. The halogen salt which forms is readily separated and the solution of thiocyano ester purified by conventional methods, such as decolorizing with charcoal, solvent extraction, or distillation.

As an acidic condensing agentin the above reaction between 1,4-endomethylene tetrahydro- A -fluorene and a halo aliphatic carboxylic acid there may e ubsed boron trifluoride and its coordination complexes with oxygenated compounds such as ethers, esters, carboxyllc acids, ketones, aldehydes, water, etc., sulfuric acid, acid esters of sulfuric acid, such as ethyl acid sulfate, sulfonic acids, such as toluene sulfonic acid, or butylsulfonic' acid, other strong acids, and the usual amphoteric metal halides with are effective as acidic catalysts such as aluminum chloride. The amount of such catalyst used need be only a small per cent of the weight of the starting hydrocarbon but may be as much as or more than a molar equivalent.

, The reaction may be performed with or without an organic solvent such as ethylene dichloride or dioxane. It may be performed at a temperature from room temperature up to 150 C. or more, although the range of about 50 C. to about C. is preferred.

According to the second method, 1,4-endomethylene tetrahydro-A -fiuorene is hydrated in the presence of a strongly acidic catalyst, such as sulfuric acid, addition and rearrangement also occurring in this reaction. The reaction, full details of which are given in application Serial No. Y

517,204, filed January 6, 19%, may be represented as follows:

Example 1 A mixture of 290 grams of chloroacetic acid, 550 grams of 1,4-endomethylene tetrahydro-A fluorene, and 20 grams of 40% sulfuric acid was stirred and-heated at 95 C. for six hours. The reaction mixture was cooled, washed with water, dried, and distilled in vacuo. The chloroacetate of endoethylene hydroxy-cyclopentanoindane distilled over at 165-170 C./ l mm. as a colorless A'mixture of 195 grams of the above ester, 65 grams of sodium thiocyanate and 200 grams of ethanol was stirred and boiled under reflux for eight hours. The resulting mixture was cooled and washed thoroughly with water. The product thus obtained was dried in vacuo at 95 0., yielding an amber-colored oil, weighing 203 grams and consisting of over 98% pure thiocyanoacetate 0f endoethylene hydroxycyclopentanoindane. odorized kerosene gave a 100% kill when tested by the Feet-Grady method as an insecticide against flies, and was free of objectionable odor or irritation.

Example 2 A mixture of 75 grams of 1,4-endomethylene tetrahydro-A -fluorene and 100 grams of aqueous 40% sulfuric acid was rapidly stirred and boiled under reflux at 120-125 C. for four and one-half hours. The mixture was cooled and the resulting A5% solution of this compound in de- -stituents in that part of the molecule.

tached to a water separator until water ceased coming over. This required about three hours. The product was cooled, washed with water, and dried in vacuo to yield the p-chloropropionate of endoethylene hydroxycyclopentanoindane as a.

pale amber-colored oil.

One-mol of this ester in an equal volume of alcohol was boiled for eight hours with 1.1 mol equivalents of potassium thiocyanate. The product wa then washed with water and dried in Example 3 Instead of the p-chloropropionic acid in Example 2, an equivalent molecular quantity of a-ChlO- roisobutyric acid may be used. The a-OhlOl'OiSO- butyrate of endoethylene hydroxycyclopentanoindane is obtained as a pale yellow oil. When heated in isopropanol olution with an equivalent amount of sodium thiocyanate it yields the corresponding a-thiocyanoisobutyrate of endoethylene hydroxy-cyclopentanoindane as a pale yellow oil, useful as a toxicant for the preparation of insecticides.

The phenyl group which is present in the molecule of the addition-rearrangement product permits the introduction of a great variety of sube One or more such substituent may be introduced into the phenyl ring. introduced include alkyl groups, such as methyl, ethyl, isopropyl, butyl, tert.butyl, octyl, isooctyl, -tetramethyl butyl, nonyl, etc., keto, such as the acetyl group, nitro, sulfonate, halogen, etc.

dark, viscous oil separated, and taken up in benas a viscous pale yellow oil which crystallizes on standing. After recrystallization from nitromethane it formed colorless crystals melting at One molecular equivalent of the above alcohol and 1.1 mols of beta-chloropropionic acid togeth-- er with 1 gram of 40% sulfuric acid was boiled in benzene solution under a reflux condenser at- I claim:

1. As a new compound, an ester of a thiocyano saturated aliphatic carboxylic acid and 3,5-endoethylene hydroxycyclopentanoindane.

2. As a new compound, an ester of a saturated thiocyano aliphatic carboxylic acid of two to Typical groups which may be 

